JP2021107514A - Polymerizable composition for optical article, and optical article - Google Patents

Abstract

To provide a polymerizable composition for an optical article that can form a photochromic layer having excellent adhesion to an adjacent layer.SOLUTION: Provided is a polymerizable composition for an optical article containing a photochromic compound, component A: an acyclic methacrylate having a molecular weight of 500 or more, and component B: a hydroxy group-containing (meth)acrylate.SELECTED DRAWING: None

Description

The present invention relates to polymerizable compositions for optical articles and optical articles.

The photochromic compound is a compound having a property of developing color under irradiation with light in a wavelength range having photoresponsiveness and fading under non-irradiation (photochromic property). As a method of imparting photochromic properties to an optical article such as a spectacle lens, a coating containing a photochromic compound and a polymerizable compound is provided on a substrate, and the coating is cured to form a cured layer (photochromic layer) having photochromic properties. Examples thereof include a method of forming (see, for example, Patent Document 1).

WO2003 / 011967

As a property desired for an optical article having the above-mentioned photochromic property, excellent adhesion between the photochromic layer and the adjacent layer can be mentioned.

One aspect of the present invention provides a polymerizable composition for an optical article capable of forming a photochromic layer having excellent adhesion to an adjacent layer.

One aspect of the present invention is
Photochromic compounds and
Component A: Acyclic methacrylate having a molecular weight of 500 or more,
Component B: Hydroxy group-containing (meth) acrylate and
Polymerizable composition for optical articles (hereinafter, also simply referred to as “composition”),
Regarding.

The composition contains the above components A and B. Thereby, the photochromic layer formed by curing this composition can exhibit excellent adhesion to the adjacent layer.

According to one aspect of the present invention, it is possible to provide a composition for an optical article capable of forming a photochromic layer having excellent adhesion to an adjacent layer. Further, according to one aspect of the present invention, it is possible to provide an optical article having a photochromic layer having excellent adhesion to an adjacent layer.

[Polymerizable composition for optical articles]
Hereinafter, the polymerizable composition for an optical article according to one aspect of the present invention will be described in more detail.

In the present invention and the present specification, the polymerizable composition means a composition containing a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. The polymerizable composition for an optical article according to one aspect of the present invention is a polymerizable composition used for producing an optical article, and can be a coating composition for an optical article. More specifically, optical It can be a coating composition for forming a photochromic layer of an article. The coating composition for an optical article means a composition applied to a base material or the like for the production of an optical article. Examples of the optical article include various lenses such as a spectacle lens and a lens for goggles, a visor portion of a sun visor, a shield member of a helmet, and the like. For example, a spectacle lens produced by applying the above composition to a lens base material becomes a spectacle lens having a photochromic layer, and can exhibit photochromic properties.

In the present invention and the present specification, the term "(meth) acrylate" is used to include acrylate and methacrylate. "Acrylate" is a compound having one or more acryloyl groups in one molecule. A "methacrylate" is a compound having one or more methacryloyl groups in one molecule. For (meth) acrylate, the functional number is the number of groups selected from the group consisting of acryloyl groups and methacryloyl groups contained in one molecule. In the present invention and the present specification, "methacrylate" means a (meth) acryloyl group containing only a methacryloyl group, and a (meth) acryloyl group containing both an acryloyl group and a methacryloyl group is an acrylate. Call. The acryloyl group may be contained in the form of an acryloyloxy group, and the methacryloyl group may be contained in the form of a methacryloyloxy group. The "(meth) acryloyl group" described below is used in the sense of including an acryloyl group and a methacryloyl group, and the "(meth) acryloyloxy group" includes an acryloyloxy group and a methacryloyloxy group. Used in the sense. Further, unless otherwise specified, the described groups may have a substituent or may be unsubstituted. When a group has a substituent, the substituents include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), a hydroxyl group, an alkoxy group (for example, an alkoxy group having 1 to 6 carbon atoms), and a halogen atom (for example, a fluorine atom). , Chlorine atom, bromine atom), cyano group, amino group, nitro group, acyl group, carboxy group and the like. Further, with respect to the group having a substituent, the "carbon number" shall mean the carbon number of the portion not containing the substituent.

<Polymerizable compound>
The composition contains at least component A and component B as a polymerizable compound. The component A and the component B will be described below.

(Component A)
Component A is an acyclic methacrylate having a molecular weight of 500 or more. In the present invention and the present specification, the term "non-cyclic" means that it does not include a cyclic structure. On the other hand, "annular" means to include an annular structure. The acyclic methacrylate refers to a monofunctional or higher methacrylate that does not contain a cyclic structure.

により示すことができ、Ｒはアルキレン基を表し、ｎはＲＯで表されるアルコキシ基の繰り返し数を示し、２以上である。Ｒで表されるアルキレン基としては、エチレン基、プロピレン基、テトラメチレン基等が挙げられる。ｎは、２以上であり、例えば３０以下、２５以下または２０以下であることができる。ポリアルキレングリコールジメタクリレートの具体例としては、ポリエチレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレート、ポリテトラメチレングリコールジメタクリレート等を挙げることができる。 Component A can be monofunctional or bifunctional or higher, preferably bifunctional or trifunctional methacrylate, more preferably bifunctional methacrylate. As the component A, polyalkylene glycol dimethacrylate can be mentioned. Polyalkylene glycol dimethacrylate is prepared by the following formula 1:

, R represents an alkylene group, n represents the number of repetitions of the alkoxy group represented by RO, and is 2 or more. Examples of the alkylene group represented by R include an ethylene group, a propylene group, and a tetramethylene group. n is 2 or more, and can be, for example, 30 or less, 25 or less, or 20 or less. Specific examples of polyalkylene glycol dimethacrylate include polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and polytetramethylene glycol dimethacrylate.

The molecular weight of component A is 500 or more. A photochromic layer formed from the above composition containing an acyclic bifunctional methacrylate (component A) having a molecular weight of 500 or more together with a component B described in detail later can exhibit high adhesion to an adjacent layer. In the present invention and the present specification, the molecular weight of the polymer adopts the structural formula determined by the structural analysis of the compound or the theoretical molecular weight calculated from the raw material charging ratio at the time of production. The molecular weight of the component A is 500 or more, preferably 510 or more, more preferably 520 or more, preferably 550 or more, more preferably 570 or more, and 600 or more. Is even more preferable, 630 or more is more preferable, and 650 or more is even more preferable. The molecular weight of the component A is preferably 2000 or less, 1500 or less, 1200 or less, 1000 or less, or 800 or less, for example, from the viewpoint of increasing the hardness of the photochromic layer.

(Component B)
Component B is a hydroxy group-containing (meth) acrylate. The number of hydroxy groups contained in one molecule of component B is 1 or more, preferably 2 or more. The number of hydroxy groups contained in one molecule of component B is preferably 4 or less, and more preferably 3 or less. The functional number of the component B is 1 or more (that is, monofunctional or more), and preferably 2 or more. Moreover, the functional number is preferably 3 or less. The component B may contain only an acryloyl group, a methacryloyl group alone, or an acryloyl group and a methacryloyl group as the (meth) acryloyl group. In one form, component B preferably contains only a methacryloyl group as the (meth) acryloyl group, i.e., a methacrylate. The molecular weight of component B can be, for example, in the range of 300 to 400, but is not limited to this range. Specific examples of component B include 2-hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxy-1-acryloyl-. 3-Metadrilloxypropane, 2-hydroxy 1-3 dimethacryloxypropane, pentaerythritol tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, monoacryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, 2- (Acryloxyoxy) ethyl 2-hydroxyethylphthalate and the like can be mentioned. Also, in one form, component B can have an amide group. Specific examples of the component B having an amide group include N- (2-hydroxyethyl) acrylamide and the like. In addition, component B can have an epoxy ester structure in one form. The epoxy ester structure is a structure formed by the reaction of an epoxy group and a carboxy group, and _{can be represented by "-CH (OH) -CH 2-} OC (= O)-". Commercially available products of component B having an epoxy ester structure include, for example, epoxy ester 40EM (manufactured by Kyoeisha Chemical Co., Ltd.), epoxy ester 70PA (manufactured by Kyoeisha Chemical Co., Ltd.), epoxy ester 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and epoxy ester 200PA (manufactured by Kyoeisha Chemical Co., Ltd.). , Epoxy ester 3002M (N) (manufactured by Kyoeisha Chemical Co., Ltd.), Epoxy ester 3002A (N) (manufactured by Kyoeisha Chemical Co., Ltd.), Epoxy ester 3000MK (manufactured by Kyoeisha Chemical Co., Ltd.), Epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

The composition may contain only component A and component B as a polymerizable compound in one form, and may contain one or more other polymerizable compounds in addition to component A and component B in another form. Can be done. Hereinafter, other polymerizable compounds that may be contained in the above composition will be illustrated.

(Other polymerizable compounds)
The components C and D exemplified below are applied to the composition without significantly affecting the color development of the photochromic layer formed from the above composition under light irradiation and the visible light transmission under non-irradiation. It is a preferable component in that it can contribute to performance improvement such as aptitude.

Ingredient C
In one form, the composition may contain an acyclic trifunctional or higher functional (meth) acrylate (component C). The component C is preferably a trifunctional (meth) acrylate, more preferably a trifunctional or tetrafunctional (meth) acrylate, and even more preferably a trifunctional (meth) acrylate. Specific examples of the component C include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolethanetri (meth) acrylate, and trimethylolpropane tri (meth) acrylate. ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetri (meth) acrylate and the like can be mentioned. The molecular weight of component C can be, for example, in the range of 200 to 400, but is not limited to this range. The component C may contain only an acryloyl group, may contain only a methacryloyl group, or may contain an acryloyl group and a methacryloyl group as the (meth) acryloyl group. In one form, the acyclic trifunctional or higher functional (meth) acrylate preferably contains only a methacryloyl group as the (meth) acryloyl group, i.e., a methacrylate.

で表される（メタ）アクリレート（成分Ｄ）を含むことができる。 Ingredient D
In one form, the composition has a molecular weight of 400 or less and has the following formula 2:

The (meth) acrylate (component D) represented by can be contained.

In Equation 2, R ¹ and R ² independently represent a hydrogen atom or a methyl group, and m represents an integer of 1 or more. m is 1 or more, and can be, for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The molecular weight of the component D is 400 or less, and from the viewpoint of further increasing the color development density when the photochromic layer develops color under light irradiation, it is preferably 350 or less, more preferably 300 or less, and more preferably 250 or less. Is more preferable. Further, the molecular weight of the component D can be, for example, 100 or more, 150 or more, or 200 or more.

The component D may contain only an acryloyl group, a methacryloyl group alone, or an acryloyl group and a methacryloyl group as the (meth) acryloyl group. In one form, component D preferably contains only an acryloyl group as the (meth) acryloyl group. Specific examples of the component E include 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate and the like.

In one form, the composition may contain one or more polymerizable compounds other than the above-mentioned components as the polymerizable compound. In the above composition, the content of the component A is preferably 50.0% by mass or more, preferably 55.0% by mass or more, assuming that the total amount of the polymerizable compound contained in the composition is 100% by mass. More preferred. In one form, the component A can be the component that occupies the largest amount among the plurality of polymerizable compounds contained in the composition. The content of component A is 90.0% by mass or less, 85.0% by mass or less, 80.0% by mass or less, and 75.0% by mass, assuming that the total amount of the polymerizable compound contained in the composition is 100% by mass. % Or less or 70% by mass or less. The composition may contain only one type of component A in one form, and may contain two or more types in the other form. When two or more kinds of component A are contained, the content rate of the above component A is the total content rate of two or more kinds. This point is the same for the content rate of other components.

Regarding component B, from the viewpoint of further improving the adhesion to the adjacent layer, the content of component B is 5.0% by mass or more, assuming that the total amount of the polymerizable compound contained in the composition is 100% by mass. It is preferably 10.0% by mass or more. Further, from the viewpoint of improving the photoresponsiveness of the photochromic compound in the photochromic layer, the content of the component B shall be 40.0% by mass or less, assuming that the total amount of the polymerizable compound contained in the composition is 100% by mass. Is preferable, and it is more preferably 35.0% by mass or less.

Regarding the component C, the content of the component C may be 0% by mass, 0% by mass or more, more than 0% by mass, and 1.0% by mass with respect to the total amount of the polymerizable compound contained in the composition. As mentioned above, it may be 3.0% by mass or more, 5% by mass or more, or 7% by mass or more. The content of the component C can be, for example, 20.0% by mass or less or 15.0% by mass or less with respect to the total amount of the polymerizable compound contained in the composition.

Regarding the component D, the content of the component D may be 0% by mass, 0% by mass or more, more than 0% by mass, and 1.0% by mass with respect to the total amount of the polymerizable compound contained in the composition. As mentioned above, it may be 3.0% by mass or more or 5.0% by mass or more. The content of the component D can be, for example, 25.0% by mass or less, 20.0% by mass or less, or 15.0% by mass or less with respect to the total amount of the polymerizable compound contained in the composition.

The content of the polymerizable compound in the above composition can be, for example, 80.0% by mass or more, 85.0% by mass or more, or 90.0% by mass or more, assuming that the total amount of the composition is 100% by mass. The content of the polymerizable compound in the above composition is, for example, 99.0% by mass or less, 95.0% by mass or less, 90.0% by mass or less, or 85.0, assuming that the total amount of the composition is 100% by mass. It can be less than or equal to mass%. In the present invention and the present specification, with respect to the content rate, the "total amount of the composition" means the total amount of all the components excluding the solvent for the composition containing the solvent. The composition may or may not contain a solvent. When a solvent is contained, any solvent can be used as a usable solvent as long as it does not hinder the progress of the polymerization reaction of the polymerizable composition.

<Photochromic compound>
The composition contains a photochromic compound together with the polymerizable compound. As the photochromic compound contained in the above composition, a known compound exhibiting photochromic properties can be used. The photochromic compound can exhibit photochromic properties to, for example, ultraviolet rays. For example, examples of the photochromic compound include compounds having a known skeleton exhibiting photochromic properties, such as a flugimid compound, a spirooxazine compound, a chromene compound, and an indeno-condensed naphthopyrane compound. The photochromic compound can be used alone or in combination of two or more. The content of the photochromic compound in the above composition can be, for example, about 0.1 to 15.0% by mass, assuming that the total amount of the composition is 100% by mass, but the content is not limited to this range.

<Other ingredients>
In addition to the polymerizable compound and the photochromic compound, the composition may contain one or more of various additives that can be usually contained in the polymerizable composition or the composition containing the photochromic compound at an arbitrary content. Examples of the additive that can be contained in the above composition include a polymerization initiator for advancing the polymerization reaction.

As the polymerization initiator, a known polymerization initiator can be used, a radical polymerization initiator is preferable, and it is more preferable that only the radical polymerization initiator is contained as the polymerization initiator. Further, as the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used, and the photopolymerization initiator is preferable from the viewpoint of advancing the polymerization reaction in a short time. Examples of the photoradical polymerization initiator include benzoyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-. Α-Hydroxyketones such as 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one; 2-benzyl-2-dimethylamino-1 Α-Aminoketones such as − (4-morpholinophenyl) -butane-1-one, 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one; 1-[ (4-Phenylthio) phenyl] -1,2-octadion-2- (benzoyl) oxime and other oxime esters; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Phenyl oxides such as 2,4,4-trimethylpentylphosphenyl oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-) Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) 4,5-diphenyl 2,4,5-Triarylimidazole dimer such as imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N'-tetramethyl-4, Benzoyl compounds such as 4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone; 2-ethylanthraquinone, phenylanthrenquinone, 2-tert-butylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10 -Kinone compounds such as phenanthraquinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone; benzoin aids such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether Tell; benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin; benzyl compounds such as benzyldimethylketal; aclysine compounds such as 9-phenylaclysine and 1,7-bis (9,9'-acridinylheptane): N- Examples thereof include phenylglycine and coumarin. Further, in the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups of the two triarylimidazole sites may give the same and symmetric compound, and give different and asymmetric compounds. May be good. Further, a thioxanthone compound and a tertiary amine may be combined, such as a combination of diethyl thioxanthone and dimethylaminobenzoic acid. Among these, α-hydroxyketone and phosphine oxide are preferable from the viewpoint of curability, transparency and heat resistance. The content of the polymerization initiator can be in the range of, for example, 0.1 to 5.0% by mass, assuming that the total amount of the composition is 100% by mass.

Further to the above composition, known additives which can be usually added to a composition containing a photochromic compound, such as a surfactant, an antioxidant, a radical trapping agent, a light stabilizer, an ultraviolet absorber, and an antioxidant. , Antistatic agents, fluorescent dyes, dyes, pigments, fragrances, plasticizers, silane coupling agents and the like can be added in any amount. Known compounds can be used as these additives.

The above composition can be prepared by sequentially mixing the various components described above at the same time or in any order.

[Optical article]
One aspect of the present invention relates to an optical article having a base material and a photochromic layer obtained by curing the above composition.
Hereinafter, the above optical article will be described in more detail.

<Base material>
The optical article can have a photochromic layer on a substrate selected according to the type of the optical article. As an example of the base material, the spectacle lens base material can be a plastic lens base material or a glass lens base material. The glass lens base material can be, for example, a lens base material made of inorganic glass. As the lens base material, a plastic lens base material is preferable from the viewpoint of being lightweight, hard to break, and easy to handle. Examples of the plastic lens base material include styrene resins such as (meth) acrylic resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, and polyether resins. , Urethane resin obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, a thiourethane resin obtained by reacting an isocyanate compound with a polythiol compound, and a (thio) epoxy compound having one or more disulfide bonds in the molecule. Examples thereof include a cured product (generally referred to as a transparent resin) obtained by curing the curable composition contained therein. As the lens base material, an undyed lens (colorless lens) may be used, or a dyed lens (dyed lens) may be used. The refractive index of the lens base material can be, for example, about 1.60 to 1.75. However, the refractive index of the lens base material is not limited to the above range, and may be within the above range or may be vertically separated from the above range. In the present invention and the present specification, the refractive index means the refractive index for light having a wavelength of 500 nm. Further, the lens base material may be a lens having a refractive power (so-called prescription lens) or a lens without refractive power (so-called prescription lens).

The spectacle lens can be various lenses such as a single focus lens, a multifocal lens, and a progressive power lens. The type of lens is determined by the surface shapes of both sides of the lens base material. Further, the surface of the lens base material may be a convex surface, a concave surface, or a flat surface. In ordinary lens substrates and spectacle lenses, the surface on the object side is convex and the surface on the eyeball side is concave. However, the present invention is not limited to this. The photochromic layer can usually be provided on the object-side surface of the lens base material, but may be provided on the eyeball-side surface.

<Photochromic layer>
The photochromic layer of the optical article is formed by applying the composition directly or indirectly on the surface of the base material via one or more other layers, and applying a curing treatment to the applied composition. Can be done. As the coating method, a known coating method such as a spin coating method or a dip coating method can be adopted, and the spin coating method is preferable from the viewpoint of coating uniformity. The curing treatment can be light irradiation and / or heat treatment, and light irradiation is preferable from the viewpoint of advancing the curing reaction in a short time. The curing treatment conditions may be determined according to the types of various components (polymerizable compounds, polymerization initiators, etc. described above) contained in the composition and the composition of the composition. The thickness of the photochromic layer thus formed is preferably in the range of, for example, 5 to 80 μm, and more preferably in the range of 20 to 60 μm.

<Primer layer>
In the above optical article, the photochromic layer can be adjacent to the base material in one form, and can be adjacent to the primer layer provided on the base material. Here, "adjacent" means that they are in direct contact with each other without interposing other layers. Examples of the primer layer include known primer layers for improving the adhesion between the photochromic layer and the base material.

Further, as one form of the primer layer, a cured layer obtained by curing the polymerizable composition for forming a primer layer containing the above-mentioned component B can also be mentioned. Hereinafter, the polymerizable composition for forming a primer layer will be described in more detail.

The component B contained in the above-mentioned polymerizable composition for forming a primer layer is as described above. In one form, the polymerizable composition for forming a primer layer may contain polyisocyanate in addition to component B. Polyisocyanate is a compound having two or more isocyanate groups in one molecule. The number of isocyanate groups contained in one molecule of polyisocyanate is 2 or more, preferably 3 or more. The number of isocyanate groups contained in one molecule of polyisocyanate can be, for example, 6 or less, 5 or less, or 4 or less. The molecular weight of the polyisocyanate can be, for example, in the range of 100 to 500, but is not limited to this range. Specific examples of the polyisocyanate include aromatic diisocyanates such as xylylene diisocyanate, phenylenedi isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane. Examples thereof include aliphatic or alicyclic diisocyanates such as diisocyanate, 1,3-bisisocyanatomethylcyclohexane and tetramethylxylylene diisocyanate. Moreover, the allophanate form, the adduct form, the biuret form, the isocyanurate form and the like of the polyisocyanate exemplified above can also be mentioned. Commercially available products of polyisocyanate include coronate HX, coronate HXR, coronate HXLV, coronate HK, coronate 2715, coronate HL, coronate L, coronate 2037, HDI, TDI, MDI (manufactured by Tosoh Corporation), Takenate 500, Takenate 600, and Duranate. 24A-100, TPA-100, TKA-100, P301-75E, Takenate D-110N, D-120N, D-127N, D-140N, D-160N, D15N, D-170N, D-170HN, D-172N , D-177N, D-178N, D-101E (manufactured by Mitsui Chemicals, Inc.) and the like.

The above-mentioned polymerizable composition for forming a primer layer can contain component B in an amount of, for example, 20.0% by mass or more, with the total amount of the composition (excluding the polymerization initiator) being 100% by mass, and 30.0% by mass. The above content is preferable, and the content is more preferably 35.0% by mass or more. Further, in the above-mentioned polymerizable composition for forming a primer layer, the content of component B can be, for example, 90.0% by mass or less, assuming that the total amount of the composition (however, excluding the polymerization initiator) is 100% by mass. , 85.0% by mass or less, and more preferably 80.0% by mass or less.

When the polymerizable composition for forming a primer layer contains polyisocyanate, the content of polyisocyanate is, for example, 10.0% by mass or more, assuming that the total amount of the composition (excluding the polymerization initiator) is 100% by mass. It is possible, preferably 15.0% by mass or more, and more preferably 20.0% by mass or more. Further, in the above-mentioned polymerizable composition for forming a primer layer, the content of polyisocyanate can be, for example, 80.0% by mass or less, assuming that the total amount of the composition (however, excluding the polymerization initiator) is 100% by mass. , 75.0% by mass or less, and more preferably 70.0% by mass or less.

The above-mentioned polymerizable composition for forming a primer layer may further contain a polymerization initiator. For the polymerization initiator, the above description can be referred to. The above-mentioned polymerizable composition for forming a primer layer may contain a polymerization initiator in a content of, for example, 0.1 to 5.0% by mass, with the total of component B and polyisocyanate as 100% by mass. ..

The polymerizable composition for forming a primer layer may or may not contain a solvent. When a solvent is contained, any solvent can be used as a usable solvent as long as it does not hinder the progress of the polymerization reaction of the polymerizable composition.

The polymerizable composition for forming a primer layer can further contain an arbitrary amount of a known additive that can be usually added to the composition for forming a primer layer. As the additive, a known compound can be used.

The above-mentioned polymerizable composition for forming a primer layer can be prepared by simultaneously or sequentially mixing the various components described above in an arbitrary order.

By applying the polymerizable composition for forming a primer layer to a base material and subjecting the applied composition to a curing treatment, the primer layer, which is a cured layer obtained by curing the polymerizable composition for forming a primer layer, is used as a base material. Can be formed on top. For the coating method, the above description can be referred to. One or more known pretreatments such as alkali treatment and UV ozone treatment can be arbitrarily applied to the surface of the base material before coating in order to clean the surface of the base material. The curing treatment can be light irradiation and / or heat treatment, and light irradiation is preferable from the viewpoint of advancing the curing reaction in a short time. The curing treatment conditions may be determined according to the types of various components contained in the above-mentioned polymerizable composition for forming a primer layer and the composition of the above-mentioned polymerizable composition for forming a primer layer.

The thickness of the primer layer can be, for example, 3 μm or more, and is preferably 5 μm or more. The thickness of the primer layer can be, for example, 15 μm or less, and is preferably 10 μm or less.

The optical article having the above-mentioned photochromic layer may or may not have one or more functional layers in addition to the above-mentioned various layers. Examples of the functional layer include layers known as functional layers of optical articles such as a protective layer for improving the durability of the optical article, an antireflection layer, a water-repellent or hydrophilic antifouling layer, and an antifogging layer. Can be done.

One form of the optical article is a spectacle lens. Further, as one form of the above optical article, a lens for goggles, a visor (eaves) portion of a sun visor, a shield member of a helmet, and the like can also be mentioned. An optical article having an antiglare function can be obtained by applying the above composition on a base material for these optical articles and subjecting the applied composition to a curing treatment to form a photochromic layer.

[glasses]
One aspect of the present invention relates to spectacles provided with a spectacle lens, which is a form of the above optical article. The details of the spectacle lens included in the spectacles are as described above. By providing the above-mentioned spectacle lens, for example, the photochromic compound contained in the photochromic layer can exert an antiglare effect like sunglasses by being irradiated with sunlight to develop a color indoors. When it returns, the photochromic compound fades and the permeability can be restored. A known technique can be applied to the structure of the frame and the like for the above-mentioned eyeglasses.

Hereinafter, the present invention will be further described with reference to Examples. However, the present invention is not limited to the embodiments shown in the examples.

を有するヒドロキシ基含有２官能メタクリレート３０質量部および成分Ｃであるトリメチロールプロパントリメタクリレート（分子量２９６）１２質量部を混合した。
こうして得られた重合性化合物の混合物に、フォトクロミック化合物（米国特許第５６４５７６７号明細書に記載の構造式で示されるインデノ縮合ナフトピラン化合物）、光ラジカル重合開始剤（ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキシド（ＩＧＭ Ｒｅｓｉｎ Ｂ．Ｖ．社製Ｏｍｎｉｒａｄ８１９））、酸化防止剤（ビス［３−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオン酸］［エチレンビス（オキシエチレン）］）、光安定化剤（セバシン酸ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル））を混合し十分に撹拌した。その後、自転公転方式撹拌脱泡装置で脱泡した。こうして、光学物品用重合性組成物（フォトクロミック層形成用コーティング組成物）を調製した。
組成物の全量を１００質量％とした上記成分の含有率は、上記重合性化合物の混合物は９４．９０質量％、フォトクロミック化合物は３．００質量％、光ラジカル重合開始剤は０．３０質量％、酸化防止剤は０．９０質量％、光安定化剤は０．９０質量％である。
上記組成物において、重合性化合物の全量を１００質量％として、成分Ａの含有率は５８．０質量％、成分Ｂの含有率は３０．０質量％、成分Ｃの含有率は１２．０質量％である。 [Glasses lens 1]
<Preparation of Polymerizable Composition for Optical Articles (Coating Composition for Forming Photochromic Layer)>
In a plastic container, 58 parts by mass of polyethylene glycol dimethacrylate (n = 14, R is an ethylene group, molecular weight 736) as component A, and the following structure as component B:

30 parts by mass of a hydroxy group-containing bifunctional methacrylate and 12 parts by mass of trimethylolpropane trimethacrylate (molecular weight 296), which is a component C, were mixed.
The mixture of the polymerizable compound thus obtained contains a photochromic compound (an indeno-condensed naphthopyrane compound represented by the structural formula described in US Pat. No. 5,645,767) and a photoradical polymerization initiator (bis (2,4,6-trimethyl). Benzoyl) Phenylphosphine oxide (IGM Resin B.V. Omnirad 819)), antioxidant (bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxy) Ethylene)]) and a light stabilizer (bis sebacate (1,2,2,6,6-pentamethyl-4-piperidyl)) were mixed and sufficiently stirred. Then, defoaming was performed with a rotation / revolution type stirring defoaming device. In this way, a polymerizable composition for optical articles (coating composition for forming a photochromic layer) was prepared.
The content of the above components with the total amount of the composition as 100% by mass was 94.90% by mass for the mixture of the above polymerizable compounds, 3.00% by mass for the photochromic compound, and 0.30% by mass for the photoradical polymerization initiator. The antioxidant is 0.90% by mass and the light stabilizer is 0.90% by mass.
In the above composition, assuming that the total amount of the polymerizable compound is 100% by mass, the content of component A is 58.0% by mass, the content of component B is 30.0% by mass, and the content of component C is 12.0% by mass. %.

を有するヒドロキシ基含有２官能アクリレート（６０質量部）をポリイソシアネートとして東ソー社製コロネート２７１５（４０質量部）と混合した。こうして得られた混合物に、混合物の全量１００質量％に対して０．２質量％の量で光ラジカル重合開始剤（ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキシド（ＩＧＭ Ｒｅｓｉｎ Ｂ．Ｖ．社製Ｏｍｎｉｒａｄ８１９））を混合し十分に撹拌した。その後、自転公転方式撹拌脱泡装置で脱泡した。こうして得られたプライマー層形成用重合性組成物を温度２５℃相対湿度５０％の環境においてプラスチックレンズ基材の凸面にスピンコート法により塗布した後、プラスチックレンズ基材上に塗布されたプライマー層形成用組成物に対して窒素雰囲気中（酸素濃度５００ｐｐｍ以下）で紫外線（波長４０５ｎｍ）を照射し、この組成物を硬化させてプライマー層を形成した。形成されたプライマー層の厚さは８μｍであった。
上記プライマー層の上に、上記で調製したフォトクロミック層形成用コーティング組成物をスピンコート法により塗布した。スピンコートは、特開２００５−２１８９９４号公報に記載の方法により行った。その後、プラスチックレンズ基材上に塗布された上記組成物に対して窒素雰囲気中（酸素濃度５００ｐｐｍ以下）で紫外線（波長４０５ｎｍ）を照射し、この組成物を硬化させてフォトクロミック層を形成した。形成されたフォトクロミック層の厚さは４０μｍであった。
こうして、フォトクロミック層を有する眼鏡レンズを作製した。
また、フォトクロミック層形成用組成物の塗布量を変えることにより、厚さ２５μｍのフォトクロミック層を有する眼鏡レンズも作製した。 <Making spectacle lenses>
A plastic lens base material (trade name EYAS manufactured by HOYA Corporation; center wall thickness 2.5 mm, radius 75 mm, S-4.00) is immersed in a 10 mass% sodium hydroxide aqueous solution (liquid temperature 60 ° C.) for 5 minutes and then pure. It was washed with water and dried. Then, a primer layer was formed on the convex surface (object side surface) of this plastic lens base material. Specifically, the following structure, which is component B:

A hydroxy group-containing bifunctional acrylate (60 parts by mass) having a polyisocyanate was mixed with Coronate 2715 (40 parts by mass) manufactured by Tosoh Corporation as a polyisocyanate. In the mixture thus obtained, a photoradical polymerization initiator (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IGM Resin B.V.) was added in an amount of 0.2% by mass based on 100% by mass of the total amount of the mixture. The company's Omnirad 819)) was mixed and thoroughly stirred. Then, defoaming was performed with a rotation / revolution type stirring defoaming device. The polymerizable composition for forming a primer layer thus obtained was applied to the convex surface of a plastic lens base material by a spin coating method in an environment of a temperature of 25 ° C. and a relative humidity of 50%, and then the primer layer was formed on the plastic lens base material. The composition was irradiated with ultraviolet rays (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less), and the composition was cured to form a primer layer. The thickness of the formed primer layer was 8 μm.
The coating composition for forming a photochromic layer prepared above was applied onto the primer layer by a spin coating method. Spin coating was performed by the method described in Japanese Patent Application Laid-Open No. 2005-218994. Then, the composition coated on the plastic lens base material was irradiated with ultraviolet rays (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less), and the composition was cured to form a photochromic layer. The thickness of the formed photochromic layer was 40 μm.
In this way, a spectacle lens having a photochromic layer was produced.
Further, by changing the coating amount of the composition for forming a photochromic layer, an spectacle lens having a photochromic layer having a thickness of 25 μm was also produced.

[Glasses lens 2]
The thickness was the same as in Example 1 except that 68 parts by mass of component A (polyethylene glycol dimethacrylate) was used and 20 parts by mass of 1,9-nonanediol diacrylate, which is component D, was used instead of component B. Two types of spectacle lenses with different values were produced.

[Evaluation of adhesion]
For each of the above spectacle lenses, the adhesion between the photochromic layer and the adjacent primer layer was evaluated by the cross-cut method according to JIS K5600-5-6: 1999.
Regarding the adhesion to the adjacent layer, the thinner the photochromic layer is usually, the more advantageous it tends to be. Therefore, it is desirable that even a thicker photochromic layer has excellent adhesion to an adjacent layer. Regarding the spectacle lens 2, in the evaluation by the cross-cut method at a thickness of 40 μm, the number of peeled squares was 10 out of 100 squares. On the other hand, with respect to the spectacle lens 1, the number of peeled squares was 2 out of 100 squares in the evaluation by the cross-cut method at a thickness of 40 μm. From the above results, it was confirmed that the photochromic layer of the spectacle lens 1 is superior in adhesion to the adjacent layer as compared with the photochromic layer of the spectacle lens 1. When both the spectacle lenses 1 and 2 had a thickness of 25 μm, the number of peeled squares was in the range of 0 to 5 out of 100 squares in the evaluation by the cross-cut method.

[Glasses lens 3]
The composition of the polymerizable composition used for forming the photochromic layer of the spectacle lens 1 was changed, and polyethylene glycol dimethacrylate (n = 14, R in the above formula 2, R is an ethylene group, molecular weight 736), which is a component A, was changed to 68. Part by mass, component B, 5 parts by mass of hydroxy group-containing bifunctional methacrylate having the structure shown above, component C, trimethylolpropanetrimethacrylate (molecular weight 296), 12 parts by mass, and component D, 1,9-nonane. The spectacle lens 3 was produced in the same manner as the spectacle lens 1 except that 5 parts by mass of the diol diacrylate was mixed.

[Glasses lens 4]
The composition of the polymerizable composition used for forming the photochromic layer of the spectacle lens 3 was changed, component B was not added, and instead, the amount of component D 1,9-nonanediol diacrylate added was 20% by mass. The spectacle lens 4 was produced in the same manner as the spectacle lens 3 except that the amount was increased in the portion.

[Performance evaluation of photochromic layer]
The transmittance (measurement wavelength: 550 nm) of each spectacle lens before the following measurement of the transmittance at the time of color development was measured by a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The transmittance measured in this way is hereinafter referred to as "initial transmittance".
After that, the photochromic layer of each spectacle lens is irradiated with light for 15 minutes (900 seconds) through an aeromas filter using a xenon lamp to develop a color of the photochromic compound in the photochromic layer. rice field. The transmittance (measurement wavelength: 550 nm) at the time of color development was measured by a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The light irradiation was carried out so that the irradiance and the permissible difference of the irradiance became the values shown in Table 1 below as specified in JIS T7333: 2005.

After measuring the above transmittance (hereinafter referred to as "transmittance at the time of color development"), the transmittance (measurement wavelength: 550 nm) has been changed from the time when the light irradiation was stopped [(initial transmittance-transmittance at the time of color development) / The time (half-life) required to reach 2] was measured. It can be judged that the smaller the half-life value measured in this way, the faster the fading rate and the better the photoresponsiveness.

The above results are shown in Table 2.

From the results shown in Table 2, it can be said that the component B does not affect the photoresponsiveness of the photochromic layer in the spectacle lens 3.

Finally, each of the above aspects will be summarized.

According to one aspect, a polymerizable composition for an optical article is provided, which comprises a photochromic compound, the component A, and the component B.

According to the above composition, a photochromic layer having excellent adhesion to an adjacent layer can be formed.

In one form, the composition can further include the component C.

In one form, the composition can further include the component D.

In one form, the composition can contain 50.0% by mass or more of component A with respect to the total amount of the polymerizable compound contained in the composition.

In one form, the composition can contain 5.0% by mass or more and 40.0% by mass or less of component B with respect to the total amount of the polymerizable compound contained in the composition.

According to one aspect of the present invention, there is provided an optical article having a base material and a photochromic layer obtained by curing the above composition.

In one form, the optical article can be a spectacle lens.

In one form, the optical article can be a goggle lens.

In one form, the optical article can be the visor portion of a sun visor.

In one form, the optical article can be a helmet shield member.

According to one aspect, spectacles provided with the above spectacle lens are provided.

Two or more of the various aspects and forms described herein can be combined in any combination.

It should be considered that the embodiments disclosed this time are exemplary in all respects and not restrictive. The scope of the present invention is shown by the scope of claims rather than the above description, and it is intended to include all modifications within the meaning and scope equivalent to the scope of claims.

The present invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets and the like.

Claims (11)

Photochromic compounds and
Component A: Acyclic methacrylate having a molecular weight of 500 or more,
Component B: Hydroxy group-containing (meth) acrylate and
A polymerizable composition for an optical article. Component C: Acyclic trifunctional or higher functional (meth) acrylate,
The polymerizable composition for an optical article according to claim 1, further comprising. Component D: The molecular weight is 400 or less, and the following formula 2:

[In Formula 2, R ¹ and R ² independently represent a hydrogen atom or a methyl group, and m represents an integer of 1 or more. ]
The polymerizable composition for an optical article according to claim 1 or 2, further comprising. The polymerizable composition for an optical article according to any one of claims 1 to 3, which contains 50.0% by mass or more of component A with respect to the total amount of the polymerizable compound contained in the composition. The polymerizable composition for an optical article according to any one of claims 1 to 4, which contains 5.0% by mass or more and 40.0% by mass or less of component B with respect to the total amount of the polymerizable compound contained in the composition. thing. With the base material
A photochromic layer obtained by curing the polymerizable composition for an optical article according to any one of claims 1 to 5.
Optical article with. The optical article according to claim 6, which is a spectacle lens. The optical article according to claim 6, which is a lens for goggles. The optical article according to claim 6, which is a visor portion of a sun visor. The optical article according to claim 6, which is a shield member of a helmet. Eyeglasses provided with the spectacle lens according to claim 7.